Emulsifying and treating agents



Patented Dec. 6, 1938 UNITED STATES 2,139,276 PATENT OFFICE EMULSIFYING TREATING AGENTS Samuel Lenher and Luther B. Arnold, Jr., Wilmington, Del., assignors to E. I. du Pont de a Nemours & Company, Wilmington, Del., a, corporation of Delaware I No Drawing. Application September 12, 1934, Serial No. 743,720

8 Claims.

This invention relates to the production of both self-emulsifying oils and textile treating agents and more particularly refers to a series of compounds, many of which were heretofore unknown, which are especially adapted for use in the textile industry and in the production of selfemulsifying mineral, animal, vegetable and syn-- thetic oils and waxes.

It is an object of this invention to produce selfemulsifying animal, vegetable, mineral and synthetic oils and waxes. A further object is to produce emulsions of the aforementioned oil-like materials which are readily prepared and exceptionally stable. A still further object is to pror duce new compounds particularly adapted for use, either alone or in admixture wth additional agents and/or assistants, in the textile industry. A still further object is to produce a new series of emulsifying agents. produce emulsions of water in various oil-like materials, said emulsions being of particular-interest in the dry cleaning and textile treating field. A

still further object is to obtain a class of compounds or substances which are suitable for softening textile fabrics. Additional objects will become apparent from a consideration of the following description and claims.

These objects are accomplished according to the herein described invention wherein organic salts of monobas'ic acids of high molecular weight, and especially amino derivatives thereof are produced. In a more restricted sense one embodiment of the invention pertains to the incorporation in oil-like materials of amine salts of monobasic acids containing at least'eight carbon atoms. In its preferred embodiment the invention is concerned with the incorporation in mineral, animal, vegetable and/or synthetic oils and/or waxes of amine derivatives having the following general formula:

wherein R represents an alkyl group or a carbocyclic or heterocyclic ring or one end oi a polymethylene chain of which R. is the other end, R."

residue of a normal primary alcohol containing from ten to eighteen carbon atoms.

The invention may be more readily understood by a consideration of the following illustrative examples:

' Example 1 In dry cleaning processes it is highly desirable to, incorporate a small amount of water in the A still further object is to.

Parts Dimethyl-cyclohexylamine-lauryl-sulfate 24 Oleyl alcohol 17 The resulting emulsion was exceptionally stable and was greatly superior in its detergent properties to the Stoddard solvent alone.

Example 2 One part of water was dispersed in 965 parts of Stoddard solvent by incorporating therein 2 parts of the following mixture:

Parts Diethyl-cyclohexylamine 9 Mono-lauryl phthalate 12 Oleyl alcohol.- 2.5

Here again the resulting emulsion was surprisingly stable and was greatly superior to the solvent alone in its detergent effect.

Example 3 ,A cotton spinning oil, which emulsified readily in water without the aid of additional reagents,

was formed by adding to light petroleum oil (sold under the trade name of Texspray Base) one part of the following mixture:

Parts Diethyl-cyclohexylamine-lauryl-sulfate 5 Oleyl alcohol 6 In place of oleyl alcohol other fatty alcohols of either a saturated or unsaturated nature as well as mixtures'thereof were used with satisfactory results.

The addition of water to the aforementioned spinning oil resulted in the production of a finely dispersed emulsion which was quite satisfactory in the processing of cotton. 1

Example 4 A rayon coning oil having desirable lubricating and softening properties was produced by mixing the following constituents:

Parts White rose oil (white paraflin oil) 86.5 Oleyl alcohol 10.0 Diethyl-cyclohexylamine-lauryl-sulfate 3.5

Dilute emulsions of this oil in water showed no separation upon standing for 30-40 hours.

In place of the emulsifying agent used in the above example the following agents'were used to obtain superior softening qualities:

Dimethyl-cyclohexylamine-lauryl-sulfate. Mono-cycloliexylamine-lauryl-sulfate.

Example 5 Textile finishing agents were prepared by dispersing one part of a mixture of one part of stearyl alcohol and 2 parts of diethylcyclohexylamine-lauryl-sulfate in 30 parts of water.

This dispersion imparted a surprisingly soft handle to textile materials treated therewith. Furthermore, the resulting emulsion was stable to boiling for more than an hour.

Example 6 A textile softening agent was prepared by mixing the following materials:

Parts Diethyl-cyclohexylamine-lauryl-sulfate e 2 Stearyl alcohol 1 White mineral oil 3 This mixture formed a clear solution which was readily extended with water to produce stable emulsions. A dilute emulsion of one part of the above mixture in 15 parts of water was stable to boiling for a period of more than an hour.

- Example 7 An emulsifying oil for the water baths of wire drawing machines was produced by mixing the following compounds-z Parts Diethyl-cyclohexylamine-lauryl-sulf ate 1 Oleyl alcohol 99 It is to be understood that the aforementioned examples are illustrative merely of the numerous uses for the class of compounds and substances comprised within the scope of the present invention. It is, furthermore, contemplated that in place of the specific emulsifying agents or mixtures thereof referred to in the aforementioned examples any one or more of the numerous additional emulsifying agents, a representative few of which will hereafter be tabulated, may be substituted. For example, in place of dimethyland diethyl-cyclohexylamine derivatives or in addition thereto other dialkyl cyclohexylamine derivatives may be used. Such compounds may contain the same or dissimilar alkyl groups. I

As previously mentioned, the amine derivatives referred to herein are of particular value in the production of self-emulsifying oils and waxes. Such oils and waxes may be obtained from diversified sources as, for example, oils and waxes obtained from petroleum, bone fat, bone grease, beef tallow, mutton tallow, spermaceti, olive oil, sesame oil, rape seed oil, Japan wax, carnauba Wax, Montan wax, etc. It will be noted that the aforementioned illustrative compounds are of mineral, vegetable and animal origin, and are not intended to be mutually exclusive of the numerous additional oils and waxes derived from similar sources. Likewise, synthetic oils and waxes are contemplated herein regardless of their method of manufacture. The aforementioned materials are referred to throughout the present specification and claims as oil-like materials.

Among the sulfuric acid esters of the higher fatty alcohols which maybe used are decyl, dodecyl, myristyl, hexadecyl, octadecyl and 9, l octadecenyl sulfates. prepared by any of the reactions well known to one familiar with the art.

The sulfuric acid esters may be converted into Example A Coconut oil is subjected to catalytic hydrogenation or sodium reduction to produce higher fatty alcohols. The resulting mixture of alcohols is fractionated to separate therefrom the lower 20% and the residual 20%, leaving the middle 60% fraction. This fraction is composed primarily of lauryl alcohol but also contains small amounts of decyl, myristyl, stearyl and cetyl alcohols.

To 300 parts of the mixture of alcohols, obtained from the aforementioned middle fraction, 160 parts of chlorsulfonic acid are added during stirring at such a rate that the temperature is maintained between 35 and 40 C. After addition of the chlorsulfonic acid the product is stirred for -l0 minutes and then added to 250 parts of diethyl cyclohexylamine at such a rate that the temperature is kept below 75 C. The mass is then stirred until it is uniform, resulting in the production of a product which is composed mainly of diethyl cyclohexylamine-lauryl sulfate.

In place of the mixture of alcohols just referred to or in addition thereto other alcohols preferably containing at least eight carbon atoms may be substituted. These alcohols are preferably normal primary alcohols which may be either saturated or unsaturated. For example, octyl, decyl, lauryl, myristyl, cetyl, stearyl, oleyl, ricinoleyl and linoleyl alcohols. Likewise, the alcohols selected may contain more than one hydroxyl group and/or double bond. While the aforementioned normal primary alcohols are preferred it is to be understood that the invention is not restricted thereto since alcohols having side chains or additional groupings substituted thereon are also contemplated. Halogenated alcohols, as for example, chlorinated alcohols of saturated and/or unsaturated origin are instances of such further substituted derivatives. A further example of such derivatives is the product produced by the introduction of an aro matic compound such as benzene at the double bond of an aliphatic alcohol of unsaturated nature. Furthermore, hydrocyclic alcohols are capable of use in accordance with the instructions of the present invention. Such hydrocyclic alcohols may be obtained conveniently by hydrogenation of aromatic hydroxylated compounds.

It is also to be understood that secondary and/or tertiary alcohols are contemplated herein.

At this point it may again be mentioned that the amine derivatives forming the subject matter of the present invention are of particular value in the production of self-emulsifying oil-like materials. The addition of a small amount of one of these amine derivatives or mixtures thereof, (in general such amount being within the range of about 0.2% to about 5%, based upon the amount These compounds may be ticular value.

hexylamine oleyl sulfate.

of oil-like material used) to mineral, animal, vegetable and/or synthetic oils and/or waxes re sults in the production of self-emulsifying oillike materials which form exceptionally stable emulsions when agitated with a dissimilar material such as water. Where the amine derivatives referred to herein do not dissolve readily in the particular oil-likematerial selected it has been found that this difficulty is efiectively overcome by adding thereto a small amount of free alcohol or mixture of alcohols. Such free alcohols are .preferably fat alcohols ranging from butanol to similar processes. A few of themore important.

of said processes are:

The production of self-emulsifying oil-like materials. v

The production of dry cleaning solutions containing a small amount of water as the dispersed phase, the continuous phase being ordinarily either a light petroleum oil or an organic fat solvent of natural or synthetic origin.

The dispersion of small amounts of water in liquid fuels in order to increase the efliciency thereof.

The production of lubricants for use in wire and tube drawing processes.

Cotton spinning oils.

Rayon coning oils.

Textile softening agents-textile finishing and treating materials generally.

The production of water paints.

The production of coating mixtures for carbon paper.

The production of pharmaceuticals.

The production of cosmetics, cold creams, etc.

In the softening of textile fabrics dialkyl cyclohexylamine derivatives of monobasic acids produced by partially esterifying sulfuric acid with normal primary alcohols preferably containing from ten-to eighteen carbon atoms are of par- A representative few of these compounds are diethyl cyclohexylamine lauryl sulfate, diethyl cyclohexylamine myristyl sulfate, diethyl cyclohexylamine cetyl sulfate, diethyl cyclohexylamine stearyl sulfate, and diethyl cyclo- It is also to be understood that the various well known homologues of the alkyl class may be substituted for one or both of the ethyl groups in the preceding tabulation. Moreover, it should be noted that in selecting the aforementioned dialkyl cyclohexylamine derivatives or mixtures thereof it is possible to dispense entirely with assistants such as free fatty alcohols, because such derivatives themselves possess valuable softening properties.

By means of the present invention self-emulsifying mineral, animal, vegetable and synthetic oils and waxes of great value are produced. Ex-

ceptionally stable water-in-oil and oil-in-water emulsions are likewise possible. The products described are quite compatible with each other and with other emulsifying agents and emulsifying assistants. An exceedingly large class of compounds possessing valuable emulsifying and related properties is now made available to the commercial arts. Many of these compounds are entirely new and are of value not only as emulsifying agents and in the textile industry but also as wetting, detergent and dispersing agents and for the multitudinous uses which such agents possess.

Asv many apparently widely diiferentembodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. A self-emulsifying oil which comprises a mineral oil having dissolved therein an aliphatic monohydric alcohol having at least 4 carbon atoms and diethyl-cyclohexylamine-dodecyl-sulfate.

2. An emulsion which comprises water as the dispersedphase and an aliphatic monohydric alcohol having at least 4 carbon atoms and mineral oil as the continuous phase, containing as an emulsifying agent methyl-cyclohexylaminedodecyl-sulfate.

3. A self-emulsifying composition which comprises a hydrocarbon material selected from the group consisting of mineral oils and waxes having dissolved therein an aliphatic monohydric alcohol having at least 4 carbon atoms and an N-dialkyl cyclohexylamine salt of a sulfuric acid ester of anormal primary aliphatic alcohol containing from 10 to 18 carbon atoms.

4. The composition of claim 3 wherein the alkyl radicals are members of the group consisting of methyl and ethyl radicals.

prises Stoddard solvent having dissolved therein from about 0.2% to about 5% by weight of an N-dialkyl cyclohexylamine salt of cetyl. sulfate and myristyl alcohoL 7. A water-in-oil emulsion which comprises water as the internal phase and a hydrocarbon material selected from the group consisting of mineral oils and waxes having dissolved therein an N-dialkyl cyclohexylamine salt of a sulfuric acid ester of a normal primary aliphatic alcohol containing from 10 to 18 carbon atoms and an aliphatic monohydric alcohol having at least 4 carbon atoms as'the other phase. I

8'. An emulsion which comprises water as the dispersed-phase and a mixture of an aliphatic monohydric alcohol having at least 4 carbon atoms and a mineral oil as the continuous phase containing as an emulsifying agent an N-dialkylcyclohexyl amine salt of a sulfuric acid ester of a normal primary aliphatic alcohol containing from 10 to 18 carbon atoms.

SAMUEL LENHER. LUTHER B. ARNOLD, JR. 

